氮化硼催化低碳烷烃氧化脱氢的活性起源探讨（英文）

页岩气的急速开采推动了以天然气替代石油的资源革命.除主组分甲烷外,天然气、页岩气中还包含大量乙烷、丙烷等低碳烷烃资源,将这些储量丰富的碳资源直接转化为烯烃等基础化学品有望革新以原油为基础的化学工业.现有烷烃催化脱氢制烯烃工艺中,直接脱氢过程吸热、热力学受限,且存在催化剂迅速失活的难题;而氧化脱氢是放热过程、无平衡限制,也无积碳等引发催化剂失活的问题,有利于提高反应效率、降低能耗,代表了更为高效和经济的新路线.但作为一个热力学爬坡过程,目前金属氧化物催化剂上烯烃产物很容易深度氧化到CO_2,选择性仍有待提高.非金属氮化硼能够有效活化低碳烷烃中的C-H键,促进烷烃氧化脱氢,并能够有效抑制深度氧化产物的生成,解决低碳烷烃临氧脱氢过程中产物易深度氧化的固有难题.本文综述了近期氮化硼在乙烷、丙烷、丁烷等低碳烷烃氧化脱氢制烯烃反应中的研究进展.以丙烷氧化脱氢为例,通过比较文献报道的几种氮化硼材料的氧化脱氢性能,发现羟基化氮化硼显示了最高的烯烃选择性和时空收率,以20.6%的丙烷转化率为基准,烯烃选择性超过90%,而时空收率可达6.8 golefin gcat~(-1) h~(-1).在此基础上,本文重点讨论了对于氮化硼材料催化活性起源的认识.主要实验事实和结论包括:氮化硼自身几乎没有氧化脱氢活性,而在烷烃氧化脱氢反应条件下存在活性诱导期;活性诱导期伴随着氮化硼边沿氧官能团化过程;氮化硼边沿B-O官能团没有脱氢活性,而B-OH官能团参与了氧化脱氢过程,辅助分子氧引发低碳烷烃脱氢反应;分子氧在羟基氮化硼边沿解离活化,反应过程中与边沿结构氧存在动态交换;氮化硼边沿羟基化定向合成过程可显著增强氧化脱氢反应活性.氮化硼作为一类新型烷烃氧化脱氢催化剂,目前正处于研究的初始阶段.因此,本文最后总结了一些关于氮化硼烷烃脱氢催化体系仍需深入研究的科学问题.     

Finding Postal Carrier Walk Paths in Mixed Graphs

The postman problem requires finding a lowest cost tour in a connected graph that traverses each edge at least once. In this paper we first give a brief survey of the literature on postman problems including, the original Chinese postman problem on undirected graphs, the windy Chinese postman problem on graphs where the cost of an arc depends on the direction the arc is transversed, the directed postman problem on graphs with directed edges, and the mixed postman problem on graphs in which there are some directed and some undirected arcs.We show how the mixed postman problem can be solved as an integer program, using the formulation of Gendreau, Laporte and Zhao, by a new row addition branch and bound algorithm, which is a modification of the column subtraction algorithm for set partitioning problems of Harche and Thompson. Computational experience shows that a slack variable heuristic is very effective in finding good solutions that are frequently optimal for these problems.     

Removable edges in a 5-connected graph and a construction method of 5-connected graphs

An edge e of a k-connected graph G is said to be a removable edge if G?e is still k-connected. A k-connected graph G is said to be a quasi (k+1)-connected if G has no nontrivial k-separator. The existence of removable edges of 3-connected and 4-connected graphs and some properties of quasi k-connected graphs have been investigated [D.A. Holton, B. Jackson, A. Saito, N.C. Wormale, Removable edges in 3-connected graphs, J. Graph Theory 14(4) (1990) 465-473; H. Jiang, J. Su, Minimum degree of minimally quasi (k+1)-connected graphs, J. Math. Study 35 (2002) 187-193; T. Politof, A. Satyanarayana, Minors of quasi 4-connected graphs, Discrete Math. 126 (1994) 245-256; T. Politof, A. Satyanarayana, The structure of quasi 4-connected graphs, Discrete Math. 161 (1996) 217-228; J. Su, The number of removable edges in 3-connected graphs, J. Combin. Theory Ser. B 75(1) (1999) 74-87; J. Yin, Removable edges and constructions of 4-connected graphs, J. Systems Sci. Math. Sci. 19(4) (1999) 434-438]. In this paper, we first investigate the relation between quasi connectivity and removable edges. Based on the relation, the existence of removable edges in k-connected graphs (k?5) is investigated. It is proved that a 5-connected graph has no removable edge if and only if it is isomorphic to K₆. For a k-connected graph G such that end vertices of any edge of G have at most k-3 common adjacent vertices, it is also proved that G has a removable edge. Consequently, a recursive construction method of 5-connected graphs is established, that is, any 5-connected graph can be obtained from K₆ by a number of θ⁺-operations. We conjecture that, if k is even, a k-connected graph G without removable edge is isomorphic to either K_k+1 or the graph H_k/2+1 obtained from K_k+2 by removing k/2+1 disjoint edges, and, if k is odd, G is isomorphic to K_k+1.     

Some class 1 graphs on <Emphasis Type="Italic">g</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript>-colorings

An edge-coloring of a graph G is an assignment of colors to all the edges of G. A g _c -coloring of a graph G is an edge-coloring of G such that each color appears at each vertex at least g(v) times. The maximum integer k such that G has a g _c -coloring with k colors is called the g _c -chromatic index of G and denoted by \(\chi\prime_{g_{c}}\)(G). In this paper, we extend a result on edge-covering coloring of Zhang and Liu in 2011, and give a new sufficient condition for a simple graph G to satisfy \(\chi\prime_{g_{c}}\)(G) = δ _g (G), where \(\delta_{g}\left(G\right) = min_{v\epsilon V (G)}\left\{\lfloor\frac{d\left(v\right)}{g\left(v\right)}\rfloor\right\}\).     

Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron‐based K‐edge XANES spectroscopy

Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K‐edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free‐ and cation‐bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K‐edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al‐saturated montmorillonite and Al‐saturated soil organic matter (SOM), but far less efficiently by hematite, Ca‐saturated montmorillonite and Ca‐saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K‐edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al‐saturated montmorillonite and Al‐saturated SOM differ from each other. They also are different from the spectra of amorphous FePO₄, amorphous or crystalline AlPO₄, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P‐retaining soil minerals in addition to spectra of free or cation‐bound IHP, AlPO₄, FePO₄ and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K‐edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented.     

原位微区同步辐射X射线荧光和近边吸收谱研究铅耐受细菌吸附-转化铅机理

为了从微观水平研究细菌生物吸附及转化铅机理,利用原位微区同步辐射X射线荧光(μ-SRXRF)及X射线吸收近边结构谱( XANES)研究云南兰坪铅锌矿区农田土壤样品中筛选的铅耐受性细菌吸附铅的分布特征及铅形态转化规律。土壤中具有铅耐受性的菌株主要为Arthrobacter sp.属(节杆菌属),采用μ-SRXRF对其吸附铅的含量进行快速简单直接分析,部分细菌吸附铅的含量高达5925μg/g,富集系数达14.8。XANES结果表明,细菌吸附 Pb 后存在形态为 PbS、(C17 H35 COO)2Pb 和 Pb5(PO4)3Cl 分别占58.0％,22.2％和19.8％,与培养基本身以有机态为主的Pb形态有明显差异,表明培养基中铅被细菌吸附后有向硫化物转化的趋势,这为研究重金属生物有效性的影响因素提供了实验参考。     

Four supramolecular isomers of dichloridobis(1,10‐phenanthroline)cobalt(II): synthesis,structure characterization and isomerization

Crystal engineering can be described as the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties. Free‐energy differences between supramolecular isomers are generally small and minor changes in the crystallization conditions may result in the occurrence of new isomers. The study of supramolecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering. Two supramolecular isomers of dichloridobis(1,10‐phenanthroline‐κ²N,N′)cobalt(II), [CoCl₂(C₁₂H₈N₂)₂], i.e. (IA) (orthorhombic) and (IB) (monoclinic), and two supramolecular isomers of dichloridobis(1,10‐phenanthroline‐κ²N,N′)cobalt(II) N,N‐dimethylformamide monosolvate, [CoCl₂(C₁₂H₈N₂)₂]·C₃H₇NO, i.e. (IIA) (orthorhombic) and (IIB) (monoclinic), were synthesized in dimethylformamide (DMF) and structurally characterized. Of these, (IA) and (IIA) have been prepared and structurally characterized previously [Li et al. (2007). Acta Cryst. E 63 , m1880–m1880; Cai et al. (2008). Acta Cryst. E 64 , m1328–m1329]. We found that the heating rate is a key factor for the crystallization of (IA) or (IB), while the temperature difference is responsible for the crystallization of (IIA) or (IIB). Based on the crystallization conditions, isomerization behaviour, the KPI (Kitajgorodskij packing index) values and the density data, (IB) and (IIA) are assigned as the thermodynamic and stable kinetic isomers, respectively, while (IA) and (IIB) are assigned as the metastable kinetic products. The 1,10‐phenanthroline (phen) ligands interact with each other through offset face‐to‐face (OFF) π–π stacking in (IB) and (IIB), but by edge‐to‐face (EF) C—H...π interactions in (IA) and (IIA). Meanwhile, the DMF molecules in (IIB) connect to neighbouring [CoCl₂(phen)₂] units through two C—H...Cl hydrogen bonds, whereas there are no obvious interactions between DMF molecules and [CoCl₂(phen)₂] units in (IIA). Since OFF π–π stacking is generally stronger than EF C—H...π interactions for transition‐metal complexes with nitrogen‐containing aromatic ligands, (IIA) is among the uncommon examples that are stable and densely packed but that do not following Etter's intermolecular interaction hierarchy.     

彩色半色调墨点边缘羽化的Clapper-Yule扩展模型

研究了墨点边缘发生羽化现象(非二值理想墨点)对印品光谱反射率的影响,为色彩预测模型的理论研究提供一个新的思路。采用二维高斯函数模拟墨点表面的形态,利用多重积分计算出墨点羽化后的体积,根据体积的恒常性即羽化前后墨点体积相等,推导出含边缘坡度因子σ的网点面积率以及含墨层相对厚度因子的油墨透射率,由此建立了一个Clapper-Yule扩展模型。模型的数值模拟结果表明墨点边缘油墨铺展所导致的网点物理扩大,增加了油墨对光的吸收,从而降低了最终的光谱反射率。采用Clapper-Yule分程模型对颜色进行预测时需考虑墨点边缘羽化所带来的物理网点扩大,该模型适用于彩色半色调印品的颜色预测与控制。     

Climb via vacancy diffusion of edge dislocations in 2D dislocation microstructures

The prevention of strength degradation of components is one of the great challenges in solid mechanics. In particular, at high temperatures material may deform even at low stresses, a deformation mode known as deformation creep. One of the microstructural mechanisms that governs deformation creep is dislocation motion due to the absorption or emission of vacancies, which results in motion perpendicular to the glide plane, called dislocation climb. However, the importance of the dislocation network for the deformation creep remains far from being understood. In this study, a climb model that accounts for the dislocation network is developed, by solving the diffusion equation for vacancies in a region with a general dislocation distribution. The definition of the sink strength is extended, to account for the contributions of neighbouring dislocations to the climb rate. The model is then applied to dislocation dipoles and dislocation pile-ups, which are dense dislocation structures and it is found that the sink strength of dislocations in a pile-up is reduced since the vacancy field is distributed between the dislocations. Finally, the importance of the results for modelling deformation creep is discussed.     

On the F. and M. Riesz theorem on wedges with edges of class <Emphasis Type="Italic">C</Emphasis><Superscript>1,α</Superscript>

This work extends the classical F. and M. Riesz theorem to measures that are boundary values of holomorphic functions defined on wedges in with edges that are in the class C ^1,α.This work was supported in part by NSF INT-0203005, CNPq and FAPESP